Adducts of silicon hydride polysiloxanes and hydrolyzable silanes having alkenyl radicals useful for rendering substrates water repellent



United States Patent 3,419,423 ADDUCTS OF SILICON HYDRIDE POLYSILOX-ANES AND HYDROLYZABLE SILANES HAV- IN G ALKENYL RADICALS USEFUL FOR REN-DERING SUBSTRATES WATER REPELLENT George J. Quaal, Springfield, Mass.,assignor to Dow Corning Corporation, Midland, Mich., a corporation ofMichigan No Drawing. Filed Oct. 9, 1964, Ser. No. 402,959 24 Claims.(Cl. 117-161) ABSTRACT OF THE DISCLOSURE A process of treating asubstrate with a siloxane copolymer and thereafter curing the treatedsubstrate to provide water repellency. The substrates can includefabrics, paper, glass, wood, leather and masonry products, among others.The siloxane copolymer has a general formula where R and R are eachalkyl, halogenated alkyl, phenyl or haloegnated phenyl, X is OR",chlorine atoms, NR O(CH OR, -OOCH, or OOCR", R" is alkyl, 0 is 1 to 3, ais 0 to 2, b is 2 to 4, m is 2 to 90 mol percent of the silicon atoms, nis to 98 mol percent of the silicon atoms, z is 0 to 88 mol percent ofthe silicon atoms, n-l-m-l-z is 6 to 2000, d, x and y are each 0 to 2,and x+y is 0 to 2.

This invention relates to siloxane copolymers which have silicon-bondedhydrogen atoms and silicon-containing moieties bonded to the siliconatoms of the siloxane co olymer chain through alkylene radicals. Thesiliconcontaining moieties have :readily hydrolyzable groups.

An object of the present invention is to provide siloxane copolymersfrom silicon hydride siloxane polymers and hydrolyzable silanes havingan alkenyl radical.

Another object is to provide a siloxane copolymer which is curablewithout a catalyst.

Another object is to provide a siloxane copolymer which is a water,repellent.

Another object is to provide a one-component Water repellent curable atroom conditions.

Other objects and advantages will become apparent from the followingdetailed description of the present invention and appended claims.

This invention relates to a siloxane copolymer of the general formulawherein R is a monovalent radical selected from the group consisting ofalkyl radicals having from 1 to 12 inclusive carbon atoms, halogenatedalkyl radicals having from 3 to 12 inclusive carbon atoms, phenylradicals and halogenated phenyl radicals; R is a monovalent radicalselected from the group consisting of alkyl radicals having from 1 to 8inclusive carbon atoms, halogenated alkyl radicals having from 3 to 8inclusive carbon atoms, phenyl radicals and halogenated phenyl radicals;X is a monovalent radical selected from the group consisting of ICC OR"radicals, chlorine atoms, NR" radicals, O(CH OR" radicals,

0 ll 0 OH radicals and radicals, wherein each R" is a monovalent alkylradical having from 1 to 3 inclusive carbon atoms, and c has a valuefrom 1 to 3 inclusive; a has an average Value f from 0 to 2 inclusive; bhas a value from 2 to 4 inclusive; m has a value such that at least 2mol percent of the silicon atoms have at least one --(CH SiR,,X radicalsand not more than mol percent of the silicon atoms have at least one (CH,SiR,,X radical; n has a value such that at least 10 mol percent of thesilicon atoms have at least one hydrogen atom bonded to a silicon atomand not more than 98 mol percent of the silicon atoms have at least onehydrogen atom bonded to a silicon atom; z has an average value of from 0to a maximum value which is such that not more than 88 mol percent ofthe silicon atoms have two R radicals per silicon atom; the sum of m+n+zis from 6 to 2000; x has an average value of from 0 to 2 inclusive; thesum of x+y is from 0 to 2 inclusive; and d has a value of from 0 to 2inclusive.

The siloxane copolymers of this invention can be either linearsiloxanes, cyclic siloxanes or mixtures of linear siloxanes and cyclicsiloxanes. The cyclic siloxanes can be composed of 2 to 90 mol percentof siloxane units of the unit formula R. O S i (CH2) s iXa 10 to 98 molpercent of siloxane units of the unit formula RSiiO and 0 to 88 molpercent of siloxane units of the unit formula R SiO. The mol percent isbased on the total moles of siloxane units present in the composition,One mole of a siloxane unit is equal to the formula weight of thesiloxane unit. Other units besides those discussed above can also bepresent in small amounts, such siloxane units as and 0 to 88 mol percentof siloxane units of the unit formula R SiO. The linear siloxanes areterminated by siloxane units of the unit formula The linear siloxanesare the preferred siloxanes of the invention. The siloxanes of thisinvention can also 3 4 be a mixture of linear and cyclic polysiloxanes.These radicals. In the mixtures can have an average formula R, R R R osucfims ix HOHMQXHL (slimm (simmsiioh units, a is 0, l or 2, preferably,a is or 1. The siloxane H I R 5 copolymer must have at least onehydrolyzable radical, X (C i H} to be readily curable, thus, 0 cannot bemore than 2.

I i-N d Rn The alkylene radical can be, -CH CH wherein d will vary fromO to 2. When d is 0, the siloxane 2 2 2 copolymers are essentiallycyclic polysiloxanes, and when 10 or CH2CH2cH2CH2 radicals thus is 2, 3or 4. d is 2, the siloxane copolymers are essentially linear Examples ofpolysiloxanes. When the value of d is between 0 and 2, I the siloxanecopolymers contain both linear polysiloxanes f and cyclic polysiloxanesin such a ratio as indicated by d. 0Si(CHi)i,siXa- Both the cyclic andlinear siloxanes can be polymerized it are in a random or blockstructure.

CH3 CH; The siloxane copolymers of this invention must con- H min bothOSiOH2CHzSi(OCH-3) OSiCH2CH2Sl(OCCH3)3 H R R, CHzCHa CsHs CH3 ObliRunitsand osliwmhslix3 OSiCHzCHzCHzSiCl OSiCHzCHaSi N n s I 3 units. Inthese units, R 15 a monovalent radical such CHZGHZCF3 CH3 01130 0 asalkyl radicals having from 1 to 12 carbon atoms, I l I I] such asmethyl, ethyl, ro l, pentyl, hexyl, octyl, OS1CH2OH2CH2GH2S1(O Hh,osicrnomsnocomcinn decyl, cyclopentyl and cyclohexyl radicals;halogenated GHzCH; CHZCHZCF3 CHQ(CH2)3CH3 0 alkyl radicals having from 3to 12 carbon atoms, such as 3,3,3-tri'fiuoropropyl, bromohexyl,chlorocyclohexyl, OSICHZCHZSICIZ OSXCHZOHZ SHOCCHG and3,3,4,4,5,5,6,6,7,7,8,8,8 tridecafiuorooctyl radicals; phenyl radicalsand halogenated phenyl radicals such and as dichlorophenyl, fiuorophenyland bromophenyl radi- OGHACI C1 cals. In these units, R is a monovalentradical such as alkyl radicals having from 1 to 8 carbon atomsosicmcflczsiofimc such as methyl, ethyl, propyl, butyl, hexyl,cyclopentyl, Examples of cyclohexyl and octyl radicals; halogenatedalkyl radicals iii IiI lil Ill: /CH2CI'I2 having from 3 to 8 carbonatoms, such as 3,3,3-trifluoro- Os-CH (VCH H OS-CH CHpropyl,ibromocyclopentyl, and 3,3,4,4,5,5,6,6,7,7,8,8,8-tri- 1 umsale 1M 20 l decafluorooctyl radicals; phenyl radicals and halogenated CHPCHphenyl radicals, such as chlorophenyl, dib romophenyl and H Hfiuorophenyl radicals. X is a monovalent radical selected 40 l, i, fromthe group consisting of OR" radicals wherein Oblong" OMCHZCI'HCF"(ml-(mac R" is a nionovalent alkyl radical, having from 1 to 3 C111carbon atoms such as methyl, ethyl, n-propyl and iso- H H propylradicals, such as methoxy, ethoxy, n-propoxy and l i isopropoxyradicals; NR radicals where R" is defined OSICHQ(CLI2)GCIIJ and osici cnc i above Such as 'N(CH3)2 N(CH2CH3)2 In the R SiO units, the R isdefined above. Examples CH3 CH3 CH3 of R SiO units are (CH SiO, (CH3)(CHCH )SiO, e slz s 5)( 3) s 2 z)( 3) 1\ i i 01 n, N CH s 11)( 3)(C6H5)(CH3CH2) 01120113 CH CH; 2 5O (CH3cH2)2SiO 3 (C I-I CD SiO, [CH(CH ](CH )S1O and cals where R" is defined above and c is 1, 2, or 3,such as OCH OCH OCH CH OCH CH The terminating siloxane units for thelinear siloxane have the unit formula -OCH CH OCH R, -OCH CH CH OCH OCHCH OCH CH CH (CH2) bSIiXH] X H SiI-I OCH2CH2OCI-I l BIS-1+5! In theterminating siloxane units, the and OCH OCH CH radicals;

I i. H H -(CI-I2)bSiX n OCR and R are fully defined above. Theterminating siloxane radic ls Where R 18 defined above Such as unitshave at least one R radical per unit and can have 0 up to 3 R radicalsper unit. The terminating siloxane l| CH3 09101120113 l CHQOHQOHH and gg unit can also have up to two hydrogen atoms bonded di rectly to thesilicon atom per unit, thus, y can have a CH3 value from 0 to 2. Theterminating siloxane unit can also radicals; chlorine atoms and have upto two I 0 R' ll l (CH3) SiX radicals per unit, thus x can have a valuefrom O to 2. The sum of x+y can vary from 0 to 2 depending upon theaverage number of hydrogen atoms, and

R. (CH2) ts ix radicals attached to the silicon atom of the terminatingsiloxane units. Examples of terminating siloxane units are 3)3 o.5, 3)20.5, 2( a) u.5 R i CHaCHQSKOCHa): [CH2OH2S1(OCCH3)3]2 (CHa)2SiO0.5 (CH3)s ms,

CH2CH3 H omomsnoon);

and HSiOu.5

| CHzCHzCF CHzCHzCHzSi H(CH CH2) SiOn.5

2000 siloxane units are not economical to prepare. The most preferredsiloxane copolymers contain from to 200 siloxane units.

The siloxane copolymers can be prepared by adding a silane of theformula where R, X, and a are defined above and e has a value of 0, 1 or2, to a mixture of a platinum catalyst and silicon hydride polysiloxaneof the formula y ms a ionw u where R, y, z, and a are defined above andp has a value such that at least 12 mol percent of the silicon atomshave at least one hydrogen atom bonded to a silicon atom. When e has avalue greater than 2, the preparation of the siloxane copolymers isdifiicult and not economical.

The silanes operable in this procedure are well known in the art andmany can be obtained commercially. Examples of silanes are CH =CHSiClCH2=CHCH2Si N The silicon hydride polysiloxanes operable in thisprocedure can be obtained commercially and are well known in the art.Examples of silicon hydride polysiloxanes are and any other combinationof siloxane units such as (CH SiO,

| l OH SiO, omomsio, O H5Si0, H2Si00.5, HsioM The platinum catalyst canbe in any form which is not basic in nature, such as platinum oncharcoal and platinum on alumina. The platinum catalyst should at alltimes contain as little water as possible, this is particularlyimportant when a small quantity of silane is used. Any platinum catalystwhich is basic will reduce the yield of product and will producepolymers other than those described by this invention.

The mixture of platinum catalyst and silicon hydride polysiloxane isusually preheated to a temperature of to 160 C., preferably to C. beforethe addition of the silane. These preheating temperatures are notcritical. The mixture need not be preheated before the addition of thesilane, but because the reaction is usually exothermic and substantiallybegins at about 110 to 120 C., preheating is advantageous. When smallquantities of silane are used, preheating is usually not necessary, butas larger quantities are used preheating becomes very desirable. Thereaction is vigorous and the silanes being relatively low boiling cancause the system to build up pressure and/or cause flooding in opensystems. The silane is thus usually added at a rate which is inverselyproportional to the quantity of silane to be added. The mixture isusually agitated during the addition. After the addition is completedthe mixture is raised to a temperature of 200 to 220 C. to insurecompletion of the reaction and then cooled to room temperature or tosome temperature less than 200 C. when the reaction is vacuum stripped.

The entire procedure is best conducted in the absence of moisture.Although this is not an absolute requirement,- the yields are higher andthe product purer when no moisture is present. Reasonable product yieldscan be obtained when only a minimum of preventive measures are used tokeep the system dry. Also the best results are obtained when the systemis blanketed with an inert gas such as nitrogen. Some oxidation canoccur at the reaction temperatures although systems in which an inertgas is not used usually have an insignificant amount of oxidation.

The silane and silicon hydride polysiloxane do not require a solvent forcarrying out the reaction, but an organic solvent can be used. When thesilicon hydride polysiloxane is of a high molecular weight, a solventsolution of the silicon hydride polysiloxane and/ or silane isparticularly advantageous as the viscosity of the system will be reducedand handling properties are improved. The organic solvent should beessentially waterfree, should not contain reactive groups such ashydroxyl radicals, and should permit the temperature of reaction to bereached. The higher temperatures can be reached either with higherboiling solvents or by using pressure.

Examples of some operable organic solvents are tolu one, xylene, naptha,organic esters such as butyl, acetate, Z-ethylhexyl acetate, acetate ofethylene glycol monomethyl ether, acetate of ethylene glycol monobutylether, and organic ketones such as methylethyl ketone and methylhexylketone.

After the reaction mixture has cooled to room temperature, any remainingunreacted silanes and/or solvent can be removed by heat and vacuumstripping. The catalyst can be removed by filtering.

The siloxane copolymers of this invention have excellent shelfstabilities. Whereas, other reactive siloxanes gradually change inproperties over a period of time these siloxane copolymers retain theirproperties such as viscosity whether they are stored with or withoutsolvent, as long as the container is sealed against outside moisture.When removed from a sealed container, they will cure to usable products.

The siloxane copolymers can be made by varying viscosities and can beused with or without solvents. These siloxanes can also be made intostable emulsions.

An outstanding feature of these siloxane copolymers is that they can beused as a one-component water repellent. These siloxane copolymers aresuperior water repellents for fabrics and can be applied to fabrics froman organic solvent solution, an aqueous emulsion, a consumer aerosolpackage or a dry cleaning medium. All of these methods of applicationprovide fabrics with good Water repellency without the use of any curingcatalyst and at room temperature. The water repellency produced on thefabric is durable and can withstand several washings. The waterrepellency and durability can be even further enhnaced by eitherheat-curing the fabric after application or by using a curing catalyst.A curing catalyst is particularly advantageous when the siloxanecopolymers are used in a dry cleaning medium.

The siloxane copolymers used as a water repellent can be applied from asolvent solution using such solvents as toluene, perchloroethylene,hexane, acetone, isopropanol, ethanol and methanol. The fabric to bemade water repellent can be dipped in the solvent solution of thesiloxane copolymer, the solvent solution of the siloxane copolymer canbe brushed on the fabric or applied in any other conventional manner.The amount of pickup of siloxane copolymer is preferably from 1 to 10weight percent, with from 1 to 3 weight percent being a morecommercially desirable range.

The siloxane copolymer can be applied to fabrics to provide waterrepellency from aqueous emulsion. The emulsions can be prepared in anyconventional manner using nonionic, anionic or cationic surfactants. Thenonionic surfactants are preferred. The most preferred surfactants arethe reaction product of ethylene oxide and acetylenic glycol, known asSurfynol 465, made by Air Reduction Chemical Company, andtrimethylnonylpoly ethylene glycol ether, known as Tergitol TMN-6. Theemulsion can be prepared to contain a. wide concentration of siloxanecopolymer. The most preferred concentration is from 5 to 40 weightpercent siloxane copolymer. The emulsion can be applied to the fabric inany conventional manner. The fabric can be immersed in an emulsion,removed and dried. The water repellency is usually good when the amountof siloxane copolymer pickup by the fabric is from 0.5 to Weight percentwith from 0.5 to 3 weight percent being a more commercially desirablerange.

The siloxane copolymer can be applied on fabrics to provide waterrepellency 'by spraying from aerosol packages. The siloxane copolymercan be put into any conventional type of aerosol package which issubstantially free from water. The siloxane copolymer can be in anysuitable organic solvent usually used with aerosol sprays such aschlorothene or perchloroethylene. Conventional spray propellents, suchas dichlorodifiuoromethane, can be used. The amount of siloxanecopolymer in the solvent solution is preferably from 1 to 20 weightpercent. A spray of from 2 to 60 seconds on an area of 0.2 to 0.6 squarefeet provides a fabric with good water repellency. Usually only from 2to 30 seconds is sufficient to get maximum protection.

The siloxane copolymers can be applied to fabrics with any conventionalcommercial dry cleaning medium. The siloxane copolymers of thisinvention are added to the conventional cleaning bath and this solutionboth cleans and treats the fabric making it water repellent. Thecommercial dry cleaning fluids and soaps can be used. The amount ofsiloxane copolymers used in the dry cleaning medium can be from 1 to 25weight percent based on the total cleaning medium.

The siloxane copolymers are useful in making fabrics water repellent,such as cotton, sateen, viscose, glass, nylon, Dacron, acetate, arnel,cellulose triacetate, polyacrylonitrile (Orlon), synthetic polyesters ofterephthalic acid and ethylene glycol; copolymers of acrylonitrile andvinylidene chloride (Dynel); copolymers of vinylchloride and vinylidenechloride; copolymers of vinylacetate and vinylchloride, wool and linen.

T he siloxane copolymers are also useful as Water repellents for paper,glass, wood, leather, masonry products and other substrates.

The most preferred siloxane copolymers which are useful for waterrepellents are siloxane copolymers of the wherein R, R, X, a, b, x, yand d are defined above; In

has a value such that at least 2 mol percent of the silicon atoms haveat least one (CH SiR,,X;, radical and not more than 35 mol percent ofthe silicon atoms have at least one (CH ,SiR' X radical; n has a valuesuch that at least 32.5 mol percent of the silicon atoms have at leastone hydrogen atom bonded to a silicon atom and not. more than 98 molpercent of the silicon atoms have at least one hydrogen atom bonded to asilicon atom; 2 has an average value of from 0 to a maximum value whichis not more than the value of n; and the sum of m-l-n'+z is from 6 to2000. The siloxane copolymers are particularly useful for waterrepellents when the mol percent of the siloxane units having (CH SiR,,Xradicals is from 2 to 35 mol percent, and when the number of R SiO unitsdoes not exceed more than one-half the total number of R SiO units andT11 RSiO units in the composition. The number of R SiO units is not morethan the number of such that it does not exceed 98 mol percent based onthe total number of moles of siloxane units. These siloxane copolymersare particularly useful for fabrics and have commercially acceptablewater repellency values.

The most preferred siloxane copolymers are those where R is methyl, R ismethyl, b is 2, a is or 1, and the sum of m1+n+z is from to 200. Thebest water repellency properties are obtained when n has a value suchthat at least 5 mol percent of the silicon atoms have at least one (CH,SiR',,X radical and not more than 20 mol percent of the silicon atomshave at least one (CH SiR X radical.

Although these siloxane copolymers have excellent water repellentproperties, particularly some of the above preferred species, thesesiloxane copolymers have wide utility. These siloxanes can be used forfabric softeners and lubricants, paper release coatings, for adhesives,particularly those with high amounts of hydrolyzable group, forelastomeric products, resinous products and room temperature curingcompositions.

Although these siloxane copolymers can be cured to durable films bycuring at room temperature without a catalyst, catalyst and heat can beused for curing and under some conditions it can be advantageous.Fabrics which have been treated with siloxane copolymers of thisinvention can be cured by conventional ironing or pressing, particularlythose which are treated by the dry cleaning process. Curing catalystswhich can be used are, for example, amines such as primary amines,secondary amines, tertiary amines and aminoorganosilicon compounds.Organic amines are well 'known in the art and can be obtainedcommercially. Examples of aminoorganosilicon compounds are such as andThe curing catalysts are preferably metal carboxylates, organic estersof titanium and zirconium, and alkyl tin carboxylates. Examples of metalcarboxylates are cadmium octoate, cadmium acetate, zinc octoate,potassium acetate, lead stearate, cobalt octoate, cobalt naphthenate,magnesium octoa-te, lead octoate, magnesium nap-hthenate and leadhexoate. Examples of organic esters of titanium and zirconium aretetraethyl titanate, tetraisopropy1'titanate, tetraisopropyl zirconate,tetroctyl titanate, tetraoctadecyl zirconate, octylene glycol titanate,glycerol zirconate, triethanolamine titanate, titanium lactate andzirconium lactate. v

Examples of the alkyl-tin-carboxylates are diethyl-tindiacetate,tributyl tin propionate, dibutyl-tin-dilactate, butyl-tin-tn'octoate,.octadecyl-tin-diacetate, trimethyl-tinstearate, dibutyl-tin-dibenzoate,and dibutyl-tin-diacetate.

The caalyst can be used in amounts normally used in curing hydrolyzablesystems such as from 0.01 to 20 weight percent of the total weight ofthe siloxane copolymer.

The siloxane copolymers can be cured by heating either with or withoutcatalyst. The temperatures can be from room temperature to 260 C. Whenheating is used it is preferred to heat atabove 30 C. and preferablyabove 40 C. Heating the' siloxane copolymers often shortens the curingtime although better results can in some cases, be obtained by curing atroom conditions.

The following examples are illustrative only and should not beconstrued'as limiting the invention which is properly delineated in theappended claims.

1 0 EXAMPLE .1

A mixture of 60.0 g. of a trimethylsilyl-endblockedmethylhydrogenpolysiloxane having a viscosity of 32.9 cs. at 25 C. and0.2 g. of 1.0 "weight percent platinum on charcoal was mixed in areaction flask equipped with an agitator, a dropping funnel and a refluxcondenser which is fitted with a drying tube and was preheated to 120 C.when the mixture reached a temperature of 120 C., 14.8 g. of CH=CHSi(OCH was added from the dropping funnel at a rate of 5 g. perminute. The temperature was maintained between 120 and 140 C. during theaddition. After the addition of the silane the temperature was raised to210 C. before cooling to 82 C. Any unreacted silane was removed byvacuum stripping at 82 C. and 1 mm. of Hg. The stripped product wasvacuum filtered through a bed of exceptionally pure diatomaceous silica,known as Super-Cel made by Celite, providing 59.6 g. of product, whichwas a trimethylsilyl-endblocked siloxane copolymer having about 10 molpercent of the units of the unit formula CH3 OSiCHzCH2Si(O CH3):

and 90 mol percent of the units of the unit formula i OSiCHa The productwas soluble in toluene, acetone, hexane and isopropanol.

An emulsion was made from the above product by dissolving 20 g. ofproduct in 20 g. of toluene and then slowly adding to this solution 40ml. of an aqueous solution of 2 weight percent oftrimethylnonylpolyethylene glycol ether, Tergitol TMN-6 and 2 weightpercent of an anionic surfactant having 3035 weight percent activeingredient and a pH of 8.6, while the solution was being mixed with ahigh speed homogenizer.

To 12 g. of the above emulsion, 185 ml. of water was added. Thisemulsion was then applied to 80 x 80 cotton print fabric by dipping andpadding. The treated cotton fabric was then conditioned for 24 hours atrelative humidity at 21 C. After the conditioning the cotton fabric wasspray rated by using the spray test as described in ASTM D58358, or thespray test of AATCC Standard Test Method 221961. The treated cottonfabric had a spray rating of 50 after 24 hours of conditioning. After anair cure of four days at room conditions, the spray rating increased toand after 16 days of air cure at room conditions, the spray ratingincreased to 90. A spray rating of 80 to 90 was obtained when thetreated and condi- ;tioned cotton fabric was cured by heating for 3minutes at 176 C.

A solvent solution .of the above product was made by dissolving 3.5 g.of the above siloxane copolymer in 120 ml. of perchloroethylene. Thissolution was applied to x 80 cotton print fabric by dipping and padding.The treated fabric was conditioned as described above. After theconditioning the fabric had a spray rating of 80. After 4 days 'of aircuring at room conditions the fabric had a spray rating of to 100, andafter 16 days of air curing the fabric had a spray rating of 100. Aftera 3-minute curing at 176 C. the treated and conditioned cotton fabrichad a spray rating of 100.

Adding 0.7 g. of dibutyl-tin-diacetate to the above solution gave aspray rating of after curing a treated and conditioned 80 x 80 cottonprint fabric for 3 minutes at 176 C.

ous siloxane copolymers. The procedure was the same except as indicatedin the following table.

13 EXAMPLE 3 The spray ratings were determined as in Example 1 on andafter 1, 3 and laundering cycles, as shown in the following table.

TABLE Spray Ratings Run No. Curing Conditions Initial spray A 'ter 1After 3 After 5 rating laundering launderings launderings 2, Example 2 3min. at 176 C 90 70-80 70 70 Example l o 100 90 80 70 3, Example 2.. .do90 80 70 70 2, Example 2 16 days at room eondi ns .90 70 70 50 Example 1do 100 70 5O 50 3, Example 2 do 90 70 70 50 EXAMPLE 6 80 x 80 cottonprint fabric treated as in Example 1 with a solution of 3.5 g. of theproducts from Example 2 in 120 The durability was determinedas inExample 5 on the same type of treated fabric except that 0.7 g. ofdibutyltin-diacetate was added as a curing'catalyst.

TAB LE Spray Ratings Run N0. Curing Conditions Initial spray After 1After 3 After 5 rating laundering launderings launderings 3 min. at 17s0 100 so 70 5of o 100 80 70 100 50-70 50 100 70 50 0 85 70 50-70 0 70 5050 EXAMPLE 7 ml. of perchloroethylene as indicated in the followingtable:

Run No. from Example 2 9o 90 so 90 70 so 50 70 50 70 EXAMPLE 4 The sprayratings as shown in the following tables, were determined as in Example1 on 80 x 80 cotton print fabric treated as in Example 1 with a solutionof 3.5 g. of the products from Example 2 and 0.7 g. ofdibutyl-tin-diacetate in ml. of perchloroethylene each having been curedfor 3 minutes at 176 C. after a conditioning of 24 hours at 65% relativehumidity and 21 C.

Run N0. from Example 2: Spray rating 1 100 2 100 3 100 4 80 5 75 6 7O 775 EXAMPLE 5 The durability of the treated fabrics were determined byobserving the water repellency as indicated by the spray rating after aspecified number of launderings. The treated fabrics were laundered in aWestinghouse Automatic Home Washer with a 40minute wash cycle, followedby drying in a Westinghouse Horne Tumble Drier with a 20- minute cycle.Each washing and drying was considered as one laundering cycle. Thewashing medium consisted of about 8 gallons of 71 C. water and 8 g. of acommercial anionic Washing detergent. Each piece of 80 x 80 cotton printfabric was treated with the siloxane copolymers in perchloroethylene asin Example 1. No curing catalyst was used. The spray ratings weredetermined before laundering The following table shows the results offabric treated with siloxane copolymers of this invention. The fabricswere treated with a solution of 3.5 g. of the siloxane copolymer, asindicated in 120 ml. of perchloroethylene. The fabrics were treated bythe procedure as defined in Example 1. Prior to the spray ratingdetermination, each piece of treated fabric was conditioned and curedfor 3 minutes at 176 C. as in Example 1.

The siloxane copolymer was added to a dry cleaning composition to addwater repellency to a fabric as it was being cleaned. The dry cleaningsolution consisted of 1600 ml. perchloroethylene, 4.0 g. of a drycleaning composition which consists of 8.95 weight percent of apolyglycol of the formula HO(C H O) C H OH where s has an average valueof 7.7, 80.50 weight percent of sodium petroleum sulfonate and 10.55weight percent of perchloroethylene. the composition is known as NorgChlor made by the Dow Chemical Company, and 27 g. of the siloxanecopolymer product of Example 2, Run No. 8. Each fabric received a 30minute wash in the above dry cleaning solution. Water repellency wasbest achieved when the fabrics were dried for 3 minutes at 176 C.,although just allowing the fabrics to drip dry did induce waterrepellency.

Spray rating, after drying Fabric dry cleaned: for 3 min. at 176 C.

EXAMPLE 9 Solutions were prepared for a spray treatment of fabric togive the fabrics a water repellent property. One 190 g.dichlorodifiuoromethane solution was composed of 10 g. of the siloxanecopoly- (B) 50 g. of the siloxane copolymer of Example 2, Run mer ofExample 2, Run No. 8, and 130 g. of perchloro- No. 8 ethylene. Anothersolution was composed of 10 g. of the 260 g. of chlorothene samesiloxane copoly-mer and 130 g. of chlorothene. Each 5 190 g. ofdichlorodifiuoromethane TABLE Spray rating Siloxane 45 min. drying 5days at room I ormulation: Time (sec) sprayed at 26 0. conditionsSprayed Back Sprayed Back side side side side A 5 0.26 80-90 70 so 10 0.50 90 70 110 so 20 0. 79 90 90 100 100 30 1. 00 00-100- 00 100 100 B 0.50 100 so 00 90 1.00 90 90 90 90 1.60 90 90 100 00 30 2.00 80-90 00 9090 C 5 0. 89 100 70 100 so of the solutions were sprayed on tan sateenfabric from a DeVilbiss Type EGA paint sprayer from 9 to 12 inches (C)g. of the siloxane copolymer of Example 2, Run

distance. About to percent of the spray was effec- No. 8 tively absorbedby the fabric. Each of the fabrics were Q 79 g. of chlorothene dried for30 minutes at 26 C. to 37 C. after having 63 g. ofdichlorodifiuoromethane TABLE Spray rating Grams of Fabric treatedsiloxane min. drying at 5 days at room copolymer 26 0. conditionssprayed Sprayed Back Sprayed Back side side side side 80 x 80 cottonprint 0. 20 100 80 100 80 Glass, Stephens 444.. 0. 27 100 100 100 100Tan sateen 0. 33 90 50 100 Viscose 0.57 90 100 Nylon 0. 18 90 80 so SpunArnel (No. 0. 22 90 8O 90 80 Spun Acetate (No. 15 0. 28 90 50 80 5OBIOVWJ wool flannel- 0. 32 8090 80 80 80 Spun Dacron (N0. 64) 0. 47 708O 50 Red sateen 0. 32 80 50 80-90 50 Olive drab twill 0. 31 70-80 50 70been sprayed. The following table provides the results Tan sateen fabricwas sprayed with each of the formulaobtained. 45 tions for varying timesfrom a distance of one foot. About 70 to 80% of the spray waseffectively absorbed by the S1 t 1f n pr y fipr yrating fabric. Thefollowing table provides the results of the 0 van SD 11110 11118 8) Kane(sec.) copolymer Sprayed Back aerosol yp p y sprayed side side 3 i2; 2%EXAMPLE 11 2 90-100 70 3 80 Various fabrics were treated by sprayingwith Formulation A of Example 10 from consumer type spray bombs.

EXAMPLE 10 The following table shows the results obtained by using Thesiloxane copolymer of Example 2, Run No. 8, was 55 the procedure ofExample 10. Each fabric was sprayed used in a water repellent treatmentof fabric from a confrom 3 to 5 seconds from one foot distance.

ventional 16 02. consumer type aerosol package formulation C being in an8 oz. package. Three formulations Were prepared and placed in aerosolpackages. 60 EXAMPLE 12 (A) 25 g. of the siloxane copolymer of Example2, Run When any of the following silanes and silicon hydride No. 8polysiloxanes are reacted in accordance with the proce- 285 g, ofchlorothene dure of Example 1, equivalent results are obtained.

TABLE Moles of silane reacted with 1 Silane Silicon Hydride Polysiloxanemole of the silicon hydride polysiloxane t 1. CHz=CHSiGl3 (SiiOM 3 i CH3Y (C5H5)z OHzOHa H CIH3 OHQCHQ 2. CHz=CHSiOCH2CH2OCHs HSiO[(SiO)2oo(SiO)35]SiH CH3 CH3 CH3 CH3 TABLE Silane Silicon HydridePolysiloxane ilt-5 ii il i y dii e polysiloxane CH CH OF; H CH3 0511 3.CHi=CHCHzSi[N(CHa)2]z H2SiO[(S iO) (SiO) 1SiHz 8 CHZCH C F CHZCH O F H4. cHg -cHCHaCHgslioi lH (CH3)3S1O (S:iO),mSi(OH 340 CH C Ha CBH HCHQCHQ 0 a C :Hu 5. CHz=CHCH2Si N HzSiO[( iO)1z(Si0) g]SiH 2 CH CH; 3(3H3 (1H3 Ce n eHm H CH3 CaH5)2 6. CHi=CHSiCh CH3Si0[(SiO) (SlO)25]SiCH25 CH3 OH;

O H 7. CHn=CHSi(0( JCHzCHa)3 (CHa)aSiO(S iO)uSi(CH3)a 4 CH2CH3 H CH; 8.OHz=CHCH2Si(OCHzCHzOH3) [(S iO)n (S i0)4]- 6 (kHzCHgCF: CeHs CdH-iCI 9.CHFOHSiO CH Siloxane copolymer having 50 mol percent (CH3S1O) units Hmol percent (OtH5S iO) units; l 15 mol percent (CHmSiO units; and 5 molpercent (CH3)3S100.5 units.

CH I 0 H H CH3 H 10. CH2=CHS i(O( )CH2CH2CH3)2 CH3S iO[(S iO)25(SiO)]SiCH3 4 (C 2)u 3 C 3 C 3 2)n a Mol percent.

EXAMPLE 13 When a solution of the siloxane copolymer of Example .1 andperchloroethylene as described in Example 1 is applied to paper,leather, wood, concrete building blocks, cement floors and fiber board,a water repellent product is formed when air dried.

EXAMPLE 14 When an aqueous emulsion of the siloxane copolymer of Example2, Run No. 8 is emulsified as described in Example 1, and applied topaper, leather, wood, concrete building blocks, and fiber board, a waterrepellent product is formed when cured by heating to 100 C.

EXAMPLE 1 5 EXAMPLE 16 When paper, leather, fiber board or concretebuilding blocks are sprayed with the mist as described in Example 10,Formulation A and then cured by heating at C.

for one hour, the substrates have water repellent properties.

EXAMPLE 17 When the dry cleaned olive drab twill of Example 8 is heatedto 260 C. for one minute equivalent results are obtained.

That which is claimed is:

1. In a process for rendering a substrate water repellent, theimprovement comprising treating said substrate with a siloxane copolymerof the general formula 19 from the group consisting of OR" radicals,chlorine atoms, NR radicals, O(CH OR" radicals,

radicals and radicals wherein each R" is a monovalent alkyl radicalhaving from 1 to 3 inclusive carbon atoms, and c has a value of from 1to 3 inclusive; a has an average value of from to 2 inclusive; b has avalue from 2 to 4 inclusive; in has a value such that at least 2 molpercent of the silicon atoms have at least one radical and not more than90 mol percent of the silicon atoms have at least one (CH SiR' Xradical; n has a value such that at least mol percent of the siliconatoms have at least one hydrogen bonded to a silicon atom and not morethan 98 mol percent of the silicon atoms have at least one hydrogen atombonded to a silicon atom; 2 has an average value of from 0 to a maximumvalue which is such that not more than 88 mol percent of the siliconatoms have two R radicals per silicon atom; the sum of mt+n+z is from 6to 2000; x has an average value of from 0 to 2 inclusive; y has anaverage value of from 0 to 2 inclusive; the sum of x+y is from 0 to 2inclusive;

and d has a value of from 0 to 2 inclusive, and thereafter curing thetreated substrate.

2. The process in accordance with claim 1 wherein the treated substrateis cured by exposing said treated substrate to air.

3. The process in accordance with claim 1 wherein the substrate is afabric.

4. The process in accordance with claim 2 wherein the substrate istreated with a solution comprising the siloxane copolymer in an organicsolvent.

5. The process in accordance with claim 2 wherein the substrate istreated with an aqueous emulsion comprising the siloxane copolymer,organic solvent, surfactant and water.

6. The process in accordance with claim 2 wherein the substrate istreated with a mist comprising the siloxane copolymer and an organicsolvent.

7; The process in accordance with claim 3 wherein the fabric is treatedwith an organic solvent solution of the siloxane copolymer.

8. The process in accordance with claim 3 wherein the fabric is treatedwith an aqueous emulsion comprising water, the siloxane copolymer and asurfactant.

9. The process in accordance with claim 3 wherein the fabric is treatedwith a mist comprising the siloxane copolymer and an organic solvent.

10. The process in accordance with claim 7 wherein the treated fabric iscured by exposing the treated fabric to air.

11. In a process for rendering a fabric water repellent,-

the improvement comprising immersing the fabric in a solution comprisingan organic solvent and a siloxane copolymer of the general formula 29atoms, halogenated alkyl radicals having from 3 to 8 inclusive carbonatoms, phenyl radicals and halogenated phenyl radicals; X is amonovalent radical selected from the group consisting of -OR" radicals,chlorine atoms, NR" radicals, O(CH OR radicals,

u OGH radicals and it OCR" radicals wherein each R" is a monovalentalkyl radical having from 1 to 3 inclusive carbon atoms, and c has avalue of from 1 to 3 inclusive; a has an average value of from 0 to 2inclusive; b has a value from 2 to 4 inclusive; m has a value such thatat least 2 mol percent of the silicon atoms have at least one .-(CH SiR'X radical and not more than mol percent of the silicon atoms have atleast one (CH SiR',,X radical; n has a value such that at least 10 molpercent of the silicon atoms have at least one hydrogen bonded to asilicon atom and not more than 98 mol percent of the silicon atoms haveat least one hydrogen atom bonded to a silicon atom; 2 has an averagevalue of from 0 to a maximum value which is such that not more than 88mol percent of the silicon atoms have two R radicals per silicon atom;the sum of m+n+z is from 6 to 2000; x has an average value of from 0 to2 inclusive; the sum of x+y is from 0 to 2 inclusive; and d has a valueof from O to 2 inclusive,

and thereafter drying said fabric by exposing said fabric to air.

12. In a process for rendering a fabric water repellent, the improvementcomprising immersing the fabric in an aqueous emulsion comprising water,a surfactant and a siloxane copolymer of the general formula wherein Ris a monovalent radical selected from the group consisting of alkylradicals having from 1 to 12 inclusive carbon atoms, halogenated alkylradicals having from 3 to 12 inclusive carbon atoms, phenyl radicals andhalogenated phenyl radicals; R is a monovalent radical selected from thegroup consisting of alkyl radicals having from 1 to 8 inclusive carbonatoms, halogenated alkyl radicals having from 3 to 8 inclusive carbonatoms, phenyl radicals and halogenated phenyl radicals; X is amonovavlent radical selected from the group consisting of OR radicals,chlorine atoms, NR" radicals, -O(CH OR" radicals,

OCH

radicals and radicals wherein each R is a monovalent alkyl radicalhaving from 1 to 3 inclusive carbon atoms, and c has a value of from 1to 3 inclusive; 0: has an average value of from 0 to 2 inclusive; 1) hasa value from 2 to 4 inclusive; in has a value such that at least 2 molpercent of the silicon atoms have at least one (CH ),,SiR' X radical andnot more than 90 mol percent of the silicon atoms have at least one (CHSiR,,X radical; n has a value such that at least 10 mol percent of thesilicon atoms have at least one hydrogen bonded to a silicon atom andnot more than 98 mol percent of the silicon'atoms have at least onehydrogen atom bonded to a silicon atom; z has an average value of from 0to a maximum value which is such that not more than 88 mol percent ofthe silicon atoms have two R radicals per silicon atom; the sum of m+n+zis from 6 to 2000; x has an average value of from to 2 inclusive; y hasan average value of from 0 to 2 inclusive; the sum of x+y is from 0 to 2inclusive; and d has a value of from 0 to 2 inclusive, and

thereafter drying said fabric by exposing said fabric to air.

13. In a progress for rendering a fabric water repellent, theimprovement comprising spraying the fabric with a mist comprising anorganic solvent and a siloxane copolymer of the general formula whereinR is a monovalent radical selected from the group consisting of alkylradicals having from 1 to 12 inclusive carbon atoms, halogenated alkylradicals having from 3 to 12 inclusive carbon atoms, phenyl radicals andhalogenated phenyl radicals; R is a monovalent radical selected from thegroup consisting of alkyl radicals having from 1 to 8 inclusive carbonatoms, halogenated alkyl radicals having from 3 to 8 inclusive carbonatoms, phenyl radicals and halogenated phenyl radicals; X is amonovalent radical selected from the group consisting of OR" radicals,chlorine atoms, -NR" radicals, O(CH OR" radicals,

radicals and II -OOR radicals wherein each R" is a monovalent alkylradical having from 1 to 3 inclusive carbon atoms, and c has a value offrom 1 to 3 inclusive; a has an average value of from 0 to 2 inclusive;b has a value of from 2 to 4 inclusive; m has a value such that at least2 mol percent of the silicon atoms have at least one (CH ,SiR',,Xradical and not more than 90 mol percent of the silicon atoms have atleast one (CH SiR',,X radical; n has a value such that at least molpercent of the silicon atoms have at least one hydrogen bonded to asilicon atom and not more than 98 mol percent of the silicon atoms haveat least one hydrogen atom bonded to a silicon atom; 1 has an averagevalue of from 0 to a maximum value which is such that not more than 88mol percent of the silicon atoms have two R radicals per silicon atom;the sum of m+n+z is from 6 to 2000; x has an average value of from 0 to2 inclusive; y has an average value of from 0 to 2 inclusive; the sum ofx-l-y is from 0 to 2 inclusive; and d has a value of from 0 to 2inclusive,

from an aerosol spray package, and thereafter drying said fabric byexposing the fabric to air.

14. In a process for rendering a fabric water repellent, the improvementcomprising washing the fabric in a dry cleaning medium comprising a drycleaning soap, a dry cleaning solvent and a siloxane copolymer of thegeneral formula wherein R is a monovalent radical selected from thegroup consisting of alkyl radicals having from 1 to 12 inclusive carbonatoms, halogenated alkyl radicals having from 3 to 12 inclusive carbonatoms, phenyl radicals and halogenated phenyl radicals; R is amonovalent radical selected from the group consisting of alkyl radicalshaving from 1 to 8 inclusive carbon atoms, halogenated alkyl radicalshaving from 3 to 8 inclusive carbon atoms, phenyl radicals andhalogenated phenyl radicals; X is a monovalent radical selected from thegroup consisting of OR" radicals, chlorine atoms, -NR" radicals, -O(CH),,OR" radicals,

ll OCH radicals and if OCR" radicals wherein each R" is a monovalentalkyl radical having from 1 to 3 inclusive carbon atoms, and c has avalue of from 1 to 3 inclusive; a has an average value of from 0 to 2inclusive; b has a value from 2 to 4 inclusive; m has a value such thatat least 2 mol percent of the silicon atoms have at least one 2 b a B-aradical and not more than mol percent of the silicon atoms have at leastone (CH SiR',-,,X radical; n has a value such that at least 10 molpercent of the silicon atoms have at least one hydrogen bonded to asilicon atom :and not more than 98 mol percent of the silicon atoms haveat least one hydrogen atom bonded to a silicon atom; 2 has an averagevalue of from 0 to a maximum value which is such that not more than 88mol percent of the silicon atoms have two R radicals per silicon atom;the sum of m+n+z is from 6 to 2000; x has an average value of from 0 to2 inclusive; y has an average value of from O'to 2 inclusive; the sum ofx-l-y is from 0 to 2 inclusive; and d has a value of from *0 to 2inclusive, and thereafter drying the fabric by exposing the fabric toair. 15. In a process for rendering a substrate water repellent, theimprovement comprising treating the substrate with a siloxane copolymerof the general formula wherein R is a monovalent radical selected fromthe group consisting of alkyl radicals having from 1 to 12 inclusivecarbon atoms, halogenated alkyl radicals having from 3 to 12 inclusivecarbon atoms, phenyl radicals and halogenated phenyl radicals, R is amonovalent radical selected from the group consisting of alkyl radicalshaving from 1 to 8 inclusive carbon atoms, halogenated alkyl radicalshaving from 3 to 8 inclusive carbon atoms, phenyl radicals andhalogenated phenyl radicals; X is a monovalent radical selected from thegroup consisting of OR" radicals, chlorine atoms, NR" radicals, O(CH OR"radicals,

if OCH radicals and II OCR radicals wherein each R" is a monovalentalkyl radical having from 1 to 3 inclusive carbon atoms, and c has avalue of from 1 to 3 inclusive; a has an average value of from O to 2inclusive, b has a value from 2 to 4 inclusive; in has a value such thatat least 2 mol percent of the silicon atoms have at least one radicaland not more than 35 mol percent of the silicon atoms have at least one-(CH ,SiR',, X radical;

n has a value such that at least 32.5 mol percent of the silicon atomshave at least one hydrogen atom bonded to a silicon atom and not morethan 98 mol percent of the silicon atoms have at least one hydrogen atombonded to a silicon atom; 1 has an average value of from to a maximumvalue which is not more than the value of n; the sum of m+n+z is from 6to 2000; x has an average value of from 0 to 2 inclusive;

y has an average value of from 0 to 2 inclusive; the

sum of x-l-y is from 0 to 2 inclusive; and d has a value of from 0 to 2inclusive, and thereafter curing said treated substrate.

16. The process in accordance with claim wherein the substrate is afabric, the fabric is treated by immersing the fabric in an emulsioncomprising water, the siloxane copolymer and a surfactant and the fabricis thereafter cured by exposing the fabric to air.

17. The process in accordance with claim 15 wherein the substrate is afabric, the fabric is treated by spraying said fabric with a mistcomprising an organic solvent and the siloxane copolymer and said fabricis thereafter cured by exposing said fabric to air.

18. The process in accordance with claim 15 wherein the substrate is afabric, the fabric is treated by dipping the fabric in a solutioncomprising an organic solvent, the siloxane copolymer and a catalystselected from the group consisting of metal carboxylates, alkyl tincarboxylates, organic amines, organosilicon amines, organic esters oftitanium and organic esters of zirconium and the fabric is thereaftercured by heating to from C. to 260 C.

19. In a process for rendering a fabric water repellent, the improvementcomprising treating the fabric with a siloxane copolymer of the generalformula wherein R is a monovalent radical selected from the groupconsisting of alkyl radicals having from 1 to 12 inclusive carbon atoms,halogenated alkyl radicals having from 3 to 12 inclusive carbon atoms,phenyl radicals and halogenated phenyl radicals, R is a monovalentradical selected from the group consisting of alkyl radicals having from1 to 8 inclusive carbon atoms, halogenated alkyl radicals having from 3to 8 inclusive carbon atoms, phenyl radicals and halogenated phenylradicals; X is a monovlent radical selected from the group consisting ofOR" radicals, chlorine atoms, NR" radicals, O(CH OR" radicals,

t -oon radicals and Ii -0 CR" radicals wherein each R" is a monovalentalkyl radical having from 1 to 3 inclusive carbon atoms, and c has avalue of from 1 to 3 inclusive; :1 'has an average value of from 0 to 2inclusive, b has a value from 2 to 4 inclusive; m has a value such thatat least 2 mol percent of the silicon atoms have at least one radicaland not more than mol percent of the silicon atoms have at least one--(CI-I SiR,,X radical; n has a value such that at least 32.5 molpercent of the silicon atoms have at least one hydrogen atom bonded to asilicon atom and not more than 98 mol percent of the silicon atoms haveat least one hydrogen atom bonded to a silicon atom; z has an averagevalue of from O to a maximum value which is not more than the value ofn; the sum of m+n+z is from 6 to 2000; x

has an average value of from 0 to 2 inclusive; y has an average value offrom 0 to 2 inclusive; the sum of x-l-y is from 0 to 2 inclusive; and dhas a value of from 0 to 2 inclusive, and thereafter drying said fabricby exposing the fabric to air.

20. The process in accordance with claim 19 wherein the fabric isimmersed in a solution comprising an organic solvent and the siloxanecopolymer.

21. The process in accordance with claim 19 wherein the fabric istreated by spraying the fabric with a mist comprising an organic solventand the siloxane copolymer from an aerosol spray package.

22. The process in accordance with claim 19 wherein the fabric istreated by spraying the fabric with a mist comprising an organic solventand the siloxane copolymer from an aerosol spray package and the fabricis thereafter dried by heating to from 30 C. to 260 C.

23. The process in accordance with claim 20 wherein the fabric is driedby heating above 30 C.

24. In a process for rendering a fabric water repellent, the miprovementcomprising Washing the fabric in a dry cleaning medium comprising a drycleaning soap, a dry cleaning solvent and a siloxane copolymer of thegeneral formula wherein R is a monovalent radical selected from thegroup consisting of alkyl radicals having from 1 to 12 inclusive carbonatoms, halogenated alkyl radicals having from 3 to 12 inclusive carbonatoms, phenyl radicals and halogenated phenyl radicals, R is amonovalent radical selected from the group consisting of alkyl radicalshaving from 1 to 8 inclusive carbon atoms, halogenated alkyl radicalshaving from 3 to 8 inclusive carbon atoms, phenyl radicals andhalogenated phenyl radicals; X is a monovalent radical selected from thegroup consisting of OR" radicals, chlorine atoms, NR" radicals, O(CH OR"radicals,

it OCH radicals and 0 I! O C RI! radicals wherein each R" is amonovalent alkyl radical having from 1 to 3 inclusive carbon atoms, andc has a value of from 1 to 3 inclusive; a has an average value of from 0to 2 inclusive, [2 has a value from 2 to 4 inclusive; m has a value suchthat at least 2 mol percent of the silicon atoms have at least oneradical and not more than 35 mol percent of the silicon atoms have atleast one (CH SiR' X radical; n has a value such that at least 32.5 molpercent of the silicon atoms have at least one hydrogen atom bonded to asilicon atom and not more than 98 mol percent of the silicon atoms haveat least one hydrogen atom bonded to a silicon atom; 1 has an averagevalue of from 0 to a maximum value which is not more than the value ofn; the sum of m+n+z is from 6 to 2000; x has an average value of from 0to 2 inclusive; y has an average value of from 0 to 2 inclusive; the sumof x-l-y is from 0 to 2 inclusive; and d has a value of from O to 2inclusive, and thereafter drying the fabric by heating the fabric tofrom 30 C. to 260- C References Cited UNITED STATES PATENTS Dennett1l7161 Dennett 117161 Cockett et a1. 117-161 Dennett 117161 Collings117161 Bailey et a1 117-161 26 9/1959 Bailey et a1. 117-161 11/1962Reeves et a1 117-135.5 3/1964 Char-reau 117161 US. Cl. X.R.

